Process of impregnating fibrous material and the material thus obtained



Patented Mar. 11, 1941 UNITED STATES.

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PATENT OFFICE .raarananmnrs sm'raa aarnus a,

Amold'B runner: and' Georg vonFinck, Frankforton-the-Main Germany, asalgnora to L G.

Farbenlndustrie Aktlengeaellachaft, Frankforton-the-Main, Germany No Drawing. Application January 8, 1938, Serial No. 184,104. In Germany January 13, 1937 12 Claims.

The present invention relates to a process of treating artificial or natural materials, such as fibers. yarns, ribbons, threads, textile fabrics and similar materials and to the material thus ob- 8 tained. It is an object of our invention to treat the said materials with one or more impregnating agents for improving their properties. It is a further object of our invention to impart water-repellent properties to the said materials.

As materials to be treated according to the present invention various products come into question, especially such as are obtained from cellulose fibers, such as cotton, viscose artificial silk, cuprammonium artificial silk, products from cellulose esters or cellulose ethers and products from animal fibers such as wool and silk, There may also be used mixed yarns or mixed fabrics from the above materials, for instance, half-wool or mixtures from wool and artificial silk staple fiber. Many other fibrous materials may, furthermore, be used, for instance, flax, hemp, jute, ramie. These materials may, according to the process of the present invention, be rendered water-repellent.

Water-proofing impregnations are known. For instance, there are obtained by treatment with parafiin and salts of alumina textile materials from which the water immediately runs of! in drops. This water-proofing eflect is, however, lost when the material is washed but once. It has already been proposed to treat textileswith solutions in organic media, or with emulsions, of derivatives of fatty acids of high molecular weight, for instance fatty acid anhydrides or chlorides 35 and thereby to make the textile water-repellent.

We have found that textile materials may be made water-repellent, with a very good success, by treating them with a solution or an emulsion of the substances obtainable according to the copending application Serial No. 168,681 filed October 12, 1937, now U. S. Patent No. 2,180,791, dated November 21, 1939, a division of application Serial No. 123,025 filed February 26, 1937, now U. S. Patent No. 2,165,956, dated July 11, 1939, in the name of Arnold Brunner, for "Condensation products and a process of preparing them.

The products to be used for the impregnation may be made as follows:

Phenols containing in the nucleus one or more aliphatic chains having at least 4 carbon atoms are treated with aqueous formaldehyde solutions and hydrogen chloride. The chloromethyl derivatives of the phenols thus formed having the formula ASH-2.01, wherein A represents a radical of a phenol substituted by aliphatic hydrocarbon radicals having at least 4 carbon atoms are caused to react with organic nitrogen bases, especially tertiary organic nitrogen bases, such as pyridine, triethylamlne or the like, the corresponding quarternary ammonium compounds being obtained in 5 the latter case. By the impregnation with the above-named compounds the textile goods are rendered waterproof so that they can be wetted by water only with difficulty. Other impregnating or finishing agents may further be added to the solution.

A great advantage of the invention resides in the fact that even after repeated washing with soap and sodium carbonate or benzine the material does not lose its water-repellent efiect. Moreover, it is a great simplification that aqueous solutions or emulsions of the treating agent may be used for the impregnation.

The above indicated fibrous materials, for instance, yarns or fabrics, are impregnated, at ordinary or elevated temperature, with aqueous solutions or emulsions of the above-mentioned nitrogen containing compounds. The excess of liquid is removed by squeezing or centrifuging and the material is then dried, preferably at an elevated temperature. The drying operation may also be performed at lower temperatures, the dry material being then exposed to higher temperatures,

Instead of aqueous solutions or emulsions there may also be used solutions in organic solvents or the treating agent may be applied to the fibrous material, without using any solvent or diluent, at ordinary or elevated temperature. It is, however, most preferable to work in aqueous solutions or emulsions.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto: the parts are by weight:

(1) 10 parts of the pyridinium compound obtained from the chloromethyl compound of the commercial mixture of isododecyl-, isotridecyland isotetradecyl-phenol are dissolved in 1000 parts of water. A fabric of cotton or viscose artificial silk is impregnated with this solution, dried at 110 C. and subsequently washed with soap and sodium carbonate. The material has a good water-repellent efiect which is not lost when the material is washed with soap and sodium carbonate or benzine. 50

(2) 10 parts of the quaternary ammonium compound obtained from the chloromethyl compound of isododecyl-phenyl and triethylamine are dissolved in 1000 parts of water. Wool or half-wool is impregnated with this solution at 60 C. and 65 dried at 140' C. A good water-repellent eiiectis obtained which is stable to washing.

" parts of para-formaldehyde.

I is

k (3) Theimpregnating agent is prepared in the I v a heterocyclic amines and subsequently heating the following way:

j'H'ydrogen chloride is led, for 15 hours, at 15" C. into a mixture of 160 parts of dodecyl-phen'ol, 'lZO-parts" of strong hydrochloric acid and 80 The resin-likeproduct formed is separated from the'mother liquor; it contains 12'.9 per cent. of chlorine.

62 parts of this product are dissolved in 100 parts of alcohol and 22 parts of methyl-aniline are added thereto. After a one hour's heating under reflux, such an amount of alcohol ois added that a solution of about 10 per cent. strength is obtained. v parts of this solution are poured into 950 parts of water. Cotton or acetate artificial silk is impregnated with the liquid and dried at 140 C. The material has properties similar to those of the fibrous material which has been treated as described in Example 1.

i (4) By substituting in Example 3 for the 950 parts of water the corresponding quantity of alcohol and impregnating the material with this solution, a similar eflect is obtained.

1 (5) 5 parts of the pyridinium compound ob tainable from chloromethyl-iso-octyiphenol are dissolved in 1000 parts of water and the solution is used for impregnating cotton, viscose artificial silk or silk. After drying at 80 C. the materi has a good water-repellent effect.

'1 (6) Dress-goods from a mixture of wool and artificial silk staple fiber (50:50), from cotton,

viscose artificial silk or acetate artificial silk or natural silk are impregnated with a solution containing per liter of water 15 grams of a conden-' sation product from chloromethyl-isobutyl-phenol and trimethyl-amine, squeezed and, alter drying at C.- 0., heated, for 20 minutes at 130 C. The material thus treated, especially light-weight artificial silk fabric, has been imparted, besides water-repellent properties, agood non-slip finish. (7) Stuff for water-proofs from wool, cotton or artificial silk is treated, for 5 minutes, with a solution containing 20 grams of a condensation product from py dine and chloromethyl-dioctyiphenol, centrifuge and dried at (L- C. 1 (8) A fabric from half-wool or half-silk is treated, for 15 minutes, with a solution containper liter of alcohol 10 grams of a condensation product from pyridine and chloromethyl-ndodecyl-phenol. squeezed, dried and subsequently heated, for 15 minutes, at C.

1 Instead of chloromethyl-n-dodecyl-phenol, there may also be used chloromethyl-iso-dodecylphenol.

1 We claim:

1 1. The process which comprises impregnating fibrous materials with organic nitrogen compounds obtained by causing phenols of the general formula A.CH2.C1, wherein A represents a radical of a phenol substituted by aliphatic hydrocarbon radicals having a least 4 carbon atoms, to react with a nitrogen base selected from the group consisting of tertiary aliphatic and tertiary heterocyclic amines and subsequently heating the impregnated material.

2. The process which comprises impregnating fibrous materials with organic nitrogen compounds obtained by causing phenols of the general formula A.CH:.Cl, wherein ,A represents a radical of a phenol substituted by one aliphatic hydro- -of a phenol substituted by aliphatic hydrocarbon sisting of tertiary aliphatic and tertiary heteromasses carbon radical having at least 4 carbon alnms',.to react with a nitrogen base selected from the group consisting of tertiary aliphatic and tertiary impregnated material.-

3 The process which comprises impregnating fibrous materials with organic nitrogen compounds obtained by causing phenols oi the general formula A.CH2.C1, wherein A represents a radical radicals having at least 4 carbon atoms, to react with pyridine and subsequently heating the impregnated material.

4. The process of water-proofing textile materials which comprises impregnating textile materials with the compound obtained by condensation' of pyridine and the chloromethyi compound of the commercial mixture of isododecyl-, isotridecyland isotetradecyl-phenol and subsequently heating the impregnated material.

. 5. The process of water-proofing textile materials which comprises impregnating textile materials with the compound obtained by condensation of pyridine and the chloromethyl compound of isododecyl-phenol and subsequently heating the impregnated material.

6. The process of water-proofing textile materials which comprises impregnating textile materials with the compound obtained by condense tion of pyridine and the chloromethyl compound of isooctyl-phenol and subsequently heating the impregnated material.

'l. Water-proof fibrous material which has been impregnated with organic nitrogen compounds obtained by causing phenols of the general formula A.CI-h.Cl, wherein A represents a radical of a phenol substituted by aliphatic hydrocarbon radicals having at least 4 carbon atoms, to react with a nitrogen base selected from the group conradicals having at least 4 carbon atoms, to react with pyridine.

i 10. Water-proof textile material which has, been impregnated with the compound obtained by. condensation of pyridine and'the chloromethyl compound of the commercial mixture of isododecyl-, isotridecyland isotetradecyl-phenol.

1i. Water-proof textile material which has been impregnated with the compound obtained by condensation of pyridine and the chloromethyl compound of isododecyl-phenol.

12. Water-proof textile material which has been impregnated with the compound obtained by condensation of pyridine and the chloromethyl compound of isooctyl-phenol. 70

ARNOLD BRUNNER. GEORJG you FINCK. 

